The present invention relates to novel crop-protecting mixtures of active ingredients having a synergistically increased microbicidal action and comprising at least two active components, and to methods of using such mixtures in crop protection, in particular for controlling and preventing the incidence of diseases.
Component I is a compound of the formula I 
in which:
X is CH or N;
R is CH3 or cyclopropyl;
Y is H, F, Cl, Br, CF3, CF3O, propargyloxy;
Z is H, F, Cl, CF3, CF3O; or
Y and Z together are a methylenedioxy, a (difluoromethylene)dioxy, an ethylenedioxy, a (trifluoroethylene)dioxy or a benzo group.
These compounds have been described in EP-A-403 618, EP-A-460 575, WO 92/18494 and other publications.
Component II is a compound selected from the group consisting of
II A) methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate (xe2x80x9cmetalaxylxe2x80x9d; GB-1 500 581), in particular its R enantiomer,
II B) methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-D-alaninate (xe2x80x9cR-metalaxylxe2x80x9d; GB-1 500 581),
II C) methyl N-(2-furoyl)-N-(2,6-xylyl)-DL-alaninate (xe2x80x9cfuralaxylxe2x80x9d; GB-1 448 810),
II D) methyl N-phenylacetyl-N-2,6-xylyl-DL-alaninate (xe2x80x9cbenalaxylxe2x80x9d; DE-29 03 612),
II E) (xc2x1)-xcex1-(2-chloro-N-2,6-xylylacetamido)-xcex3-butyrolactone (xe2x80x9cofuracexe2x80x9d; U.S. Pat. No. 4,141,989),
II F) 2-methoxy-N-(2-oxo-1,3-oxazolidin-3-yl)-acet-2xe2x80x2,6xe2x80x2-xylidide (xe2x80x9coxadixylxe2x80x9d; GB-P. 2 058 059),
II G) 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea, (xe2x80x9ccymoxanilxe2x80x9d; U.S. Pat. No. 3,957,847) and
II H) manganese ethylenebis(dithiocarbamate) polymer zinc complex (xe2x80x9cmancozebxe2x80x9d; U.S. Pat. No. 2,974,156).
The invention furthermore relates to mixtures in which in component I of the formula I:
X is CH or N;
R is CH3 or cyclopropyl;
Y is H, F, Cl, Br, CF3, CF3O, propargyloxy;
Z is H, F, Cl; or
Y and Z together are a methylenedioxy, a (difluoromethylene)dioxy, an ethylenedioxy, a (trifluoroethylene)dioxy or a benzo group; and in which component II is a compound selected from the group consisting of
II A) methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate (xe2x80x9cmetalaxylxe2x80x9d), in particular its R enantiomer,
II B) methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-D-alaninate (xe2x80x9cR-metalaxylxe2x80x9d),
II C) methyl N-(2-furoyl)-N-(2,6-xylyl)-DL-alaninate (xe2x80x9cfuralaxylxe2x80x9d),
II D) methyl N-phenylacetyl-N-2,6-xylyl-DL-alaninate (xe2x80x9cbenalaxylxe2x80x9d),
II E) (xc2x1)-xcex1-(2-chloro-N-2,6-xylylacetamido)-xcex3-butyrolactone (xe2x80x9cofuracexe2x80x9d),
II F) 2-methoxy-N-(2-oxo-1,3-oxazolidin-3-yl)-acet-2xe2x80x2,6xe2x80x2-xylidide (xe2x80x9coxadixylxe2x80x9d), and
II G) 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea (xe2x80x9ccymoxanilxe2x80x9d).
Surprisingly, it has emerged that in the prevention and control of plant diseases the mixtures according to the invention, of components I and II, not only exert a mutually complementary action against a variety of target pathogens or a purely additive action against the same pathogens, but that they display a pronounced, synergistically increased action.
Advantageous mixing ratios of the two active ingredients are I:II=25:1 to 1:20, preferably I:II=20:1 to 1:10 and 12:1 to 1:8.
Particularly advantageous mixing ratios are
I:IIA=10:1 to 1:10
I:IIB=10:1 to 1:8
I:IIC=6:1 to 1:8
I:IID=8:1 to 1:4
I:IIE=10:1 to 1:6
I:IIF=10:1 to 1:8
I:IIG=10:1 to 1:5
I:IIH=1:30 to 1:1
Preferred two-component mixtures are those in which component I is selected from the group consisting of the following compounds:
(01) methyl 3-methoxy-2-[xcex1-{[(xcex1-cyclopropyl-3-trifluoromethylbenzyl)imino]oxy}- o-tolyl]acrylate;
(02) methyl 3-methoxy-2-[xcex1-{[(xcex1-cyclopropyl-3,4-(difluoromethylenedioxy)benzyl)- imino]oxy}-o-tolyl]acrylate;
(03) methyl 2-[xcex1-{[(xcex1-methyl-3-bromobenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(04) methyl 2-[xcex1-{[(xcex1-cyclopropyl-3,4-methylenedioxybenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(05) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-3-propargyloxybenzyl)imino]oxy}-o-tolyl]acrylate;
(06) methyl 2-[xcex1-{[(xcex1-methyl-3,4-(difluoromethylenedioxy)benzyl)imino]-oxy}- o-tolyl]glyoxylate O-methyloxime;
(07) methyl 3-methoxy-2-[xcex1-{[(xcex1-cyclopropyl-3,4-methylenedioxybenzyl)imino]oxy}- o-tolyl]acrylate;
(08) methyl 2-[xcex1-{[(xcex1-methyl-3-propargyloxybenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(09) methyl 2-[xcex1-{[(xcex1-cyclopropyl-4-fluorobenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(10) methyl 2-[xcex1-{[(xcex1-methyl-4-fluoro-3-trifluoromethylbenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(11) methyl 3-methoxy-2-[xcex1-{[(1-(xcex2-naphthyl)ethyl)imino]oxy}-o-tolyl]acrylate;
(12) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-3,4-methylenedioxybenzyl)imino]oxy}- o-tolyl]acrylate;
(13) methyl 2-[xcex1-{[(xcex1-methyl-3-chlorobenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(14) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-3,4-ethylenedioxybenzyl)imino]oxy}- o-tolyl]acrylate;
(15) methyl 2-[xcex1-{[(xcex1-cyclopropyl-4-chlorobenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(16) methyl 3-methoxy-2-[xcex1-{[(xcex1-cyclopropyl-3-chlorobenzyl)imino]oxy}- o-tolyl]acrylate;
(17) methyl 2-[xcex1-{[(xcex1-cyclopropyl-3-trifluoromethylbenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(18) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-3-trifluoromethoxybenzyl)imino]oxy}- o-tolyl]acrylate;
(19) methyl 2-[xcex1-{[(xcex1-methyl-3,4-methylenedioxybenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(20) methyl 2-[xcex1-{[(xcex1-cyclopropyl-3,4-(difluoromethylenedioxy)benzyl)imino]oxy}- o-tolyl]glyoxylate O-methyloxime;
(21) methyl 2-[xcex1-{[(xcex1-methyl-3,4-ethylenedioxybenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(22) methyl 3-methoxy-2-[xcex1-{[(1-(2,3-dihydro-2,2,3-trifluoro- 1,4-benzodioxan-6-yl)ethyl)imino]oxy}-o-tolyl]acrylate;
(23) 2-[(xcex1-{[(1-(2,3-dihydro-2,2,3-trifluoro-1,4-benzodioxan-6-yl)ethyl)imino]oxy}- o-tolyl]glyoxylate O-methyloxime;
(24) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-3-trifluoromethylbenzyl)imino]oxy}- o-tolyl]acrylate;
(25) methyl 2-[xcex1-{[(xcex1-methyl-4-chlorobenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(26) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-4-chlorobenzyl)imino]oxy}-o-tolyl]acrylate;
(27) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-3-bromobenzyl)imino]oxy}-o-tolyl]acrylate;
(28) methyl 2-[xcex1-{[(1-(xcex2-naphthyl)ethyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(29) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-3,4-(difluoromethylenedioxy)benzyl)- imino]oxy}-o-tolyl]acrylate;
(30) methyl 3-methoxy-2-[xcex1-{[(xcex1-cyclopropyl-4-fluorobenzyl)imino]oxy}- o-tolyl]acrylate;
(31) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-4-fluoro-3-trifluoromethylbenzyl)imino]oxy}- o-tolyl]acrylate;
(32) methyl 2-[xcex1-{[(xcex1-methyl-3-trifluoromethoxybenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(33) methyl 2-[xcex1-{[(xcex1-cyclopropyl-3-chlorobenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(34) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-3-chlorobenzyl)imino]oxy}-o-tolyl]acrylate;
(35) methyl 2-[xcex1-{[(xcex1-methyl-3-trifluoromethylbenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(36) methyl 3-methoxy-2-[xcex1-{[(xcex1-cyclopropyl-4-chlorobenzyl)imino]oxy}- o-tolyl]acrylate;
(37) methyl 2-[xcex1-[{[(xcex1-cyclopropyl-4-trifluoromethylbenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(38) methyl 2-[xcex1-{[(xcex1-cyclopropyl-4-trifluoromethoxybenzyl)imino]oxy}- o-tolyl]glyoxylate O-methyloxime.
The following are particularly preferred amongst these:
(25) methyl 2-[xcex1-{[(xcex1-methyl-4-chlorobenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(24) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-3-trifluoromethylbenzyl)imino]oxy}- o-tolyl]acrylate;
(32) methyl 2-[xcex1-{[(xcex1-methyl-3-trifluoromethoxybenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(12) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-3,4-methylenedioxybenzyl)imino]oxy}-o-tolyl]- acrylate;
(09) methyl 2-[xcex1-{[(xcex1-cyclopropyl-4-fluorobenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(26) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-4-chlorobenzyl)imino]oxy}-o-tolyl]acrylate;
(18) methyl 3-methoxy-2-[xcex1-{[(xcex1-methyl-3-trifluoromethoxybenzyl)imino]oxy}- o-tolyl]acrylate;
(35) methyl 2-[xcex1-{[(xcex1-methyl-3-trifluoromethylbenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(15) methyl 2-[xcex1-{[(xcex1-cyclopropyl-4-chlorobenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(36) methyl 3-methoxy-2-[xcex1-{[(xcex1-cyclopropyl-4-chlorobenzyl)imino]oxy}- o-tolyl]acrylate;
(37) methyl 2-[xcex1-{[(xcex1-cyclopropyl-4-trifluoromethylbenzyl)imino]oxy}-o-tolyl]glyoxylate O-methyloxime;
(38) methyl 2-[xcex1-{[(xcex1-cyclopropyl-4-trifluoromethoxybenzyl)imino]oxy}- o-tolyl]glyoxylate O-methyloxime.
Particularly advantageous mixtures result when a component of the formula I is employed with either metalaxyl as component II, but in particular with the enantiomeric R-metalaxyl II B in at least 85% pure form (remainder S-enantiomer).
Other preferred mixtures are those in which component II is cymoxanil or mancozeb.
Also advantageous are mixtures of components I and II which comprise mancozeb as an additional, third component.
The active ingredient mixtures I+II according to the invention have highly advantageous properties protecting plants against the incidence of disease. Using the present active ingredient mixtures, the microorganisms which are found on plants or parts of plants (fruits, flowers, foliage, stalks, tubers, roots) of a variety of crops of useful plants can be contained or destroyed, and even parts of plants which grow at a later point in time remain unharmed by such microorganisms. They can also be used as seed-dressing materials for the treatment of plant propagation material, in particular seed (fruits, tubers, kernels) and nursery plants (for example rice) for protecting them against fungal infections and against soil-borne phytopathogenic fungi. The active ingredient mixtures according to the invention are distinguished by the fact that they are well tolerated by plants and by being environmentally friendly.
As a result of the presence of typical preparations for controlling Oomycetes (for example Phytophthora, Peronospora, Bremia, Pythium, Plasmopara) as component II, the mixtures according to the invention are distinguished by a high efficacy against these pests. However, the active ingredient mixtures are furthermore active against the phytopathogenic fungi which belong to the following classes: Ascomycetes (for example Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (for example the species Hemileia, Rhizoctonia, Puccinia); and Fungi imperfecti (for example Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and, in particular, Pseudocercosporella herpotrichoides).
Examples of plant species which are suitable as target crops for the indications disclosed here are, within the scope of the present invention, the following: cereals (wheat, barley, rye, oats, rice, sorghum and related species); beet (sugar and fodder beet); pomaceous fruit, stone fruit, soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soya); oil crops (oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa, groundnuts); cucurbits (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, tangerines); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, bell peppers); Lauraceae (avocado, Cinnamonum, camphor) or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, grapevines, hops, Musaceae and latex plants, and also ornamentals (flowers, shrubs, deciduous trees and coniferous trees such as conifers). This enumeration is not limiting.
The active ingredient mixtures according to the invention are particularly advantageous for use in crops which are endangered by Oomycetes, i.e. those which are damaged by various species of downy mildew. These crops include grapevines, potatoes, tobacco, vegetables (for example tomatoes, courgettes, cucumbers, avocados) and fruit such as citrus fruit; hops, sugar beet, bananas, maize, ornamental lawn (turf) and others. Propagation material (such as seed) of leguminous plants (peas, beans, lentils), of maize, sorghum and sunflowers can furthermore be protected with the active ingredient mixtures, in particular against attack by Peronosporaceae. In addition, however, these mixtures can also be employed advantageously in other crops, especially in cereals such as wheat and barley, as already mentioned above.
The mixtures of the active ingredients of the formulae I and II are usually used in the form of combinations. The active ingredients of the formulae I and II can be applied to the area or plant to be treated either simultaneously, or one after the other on the same day, if desired together with other carriers, surfactants or other application-enhancing additives conventionally used in the art of formulation. Suitable carriers and additives can be solid or liquid and are those substances which are expedient in the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and fertilizers.
A preferred method of applying an active ingredient mixture which comprises in each case at least one of these active ingredients I and II is application to the aerial parts of the plants, especially the foliage (foliar application). Number and rates of application depend on the biological and climatic environment of the pathogen. Alternatively, the active ingredient can reach the plant via the soil or the water through the root system (systemic action), by drenching the locus of the plant with a liquid preparation (for example in rice growing) or by incorporating the substances into the soil in solid form, for example in the form of granules (soil application). The compounds of the formulae I and II can also be applied to seed kernels for the purposes of seed treatment (coating), either by soaking the tubers or kernels in succession with a liquid preparation of an active ingredient or by coating them with a pre-combined moist or dry preparation. In addition, other types of application to plants are possible in specific cases, for example the specific treatment of buds or the fruiting heads. The compounds of the combination are employed as pure active ingredients or, preferably, together with the auxiliaries conventionally used in the art of formulation, and they are therefore processed in a known manner to give, for example, emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, or by means of encapsulations, for example in polymers. The application methods, such as spraying, atomizing, dusting, scattering, brushing or pouring, and the nature of the compositions, are selected to suit the intended aims and the prevailing circumstances. Advantageous rates of application of the active ingredient mixture are generally 20 g to 1000 g of a.i./ha, in particular 50 g to 800 g of a.i./ha, particularly preferably 100 g to 700 g of a.i./ha. The rates of application for seed treatment are 0.5 g-800 g, preferably 5 g-100 g, of a.i. per 100 kg of seed.
The formulations are prepared in a known manner, for example by intimately mixing and/or grinding the active ingredients with extenders, for example with solvents, solid carriers, and, if appropriate, surface-active compounds (surfactants).
The following are possible solvents: aromatic hydrocarbons, preferably the fractions C8 to C12, for example xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and epoxidized or unepoxidized vegetable oils, such as epoxidized coconut oil or soya oil; or water.
Solid carriers which are generally used, for example for dusts and dispersible powders, are ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly disperse silica or highly disperse absorptive polymers. Possible particulate, adsorptive carriers for granules are the porous types, for example pumice, brick, grit, sepiolite or bentonite, or non-sorptive carrier materials, for example calcite or sand. In addition, a large number of pregranulated materials of inorganic or organic nature can be used such as, in particular, dolomite or comminuted plant residues.
Depending on the nature of the active ingredients of the formulae I and II to be formulated, surface-active compounds which are suitable are non-ionic, cationic and/or anionic surfactants which have good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as meaning mixtures of surfactants.
Particularly advantageous adjuvants which enhance application are furthermore natural or synthetic phospholipids from the series of the cephalins and lecithins, for example phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerine, lysolecithin.
As a rule, the agrochemical preparations comprise 0.1 to 99%, in particular 0.1 to 95%, of active ingredients of the formulae I and II, 99.9 to 1%, in particular 99.9 to 5%, of a solid or liquid additive and 0 to 25%, in particular 0.1 to 25%, of a surfactant.
While concentrated compositions are more preferred as commercial products, the end user tends to use dilute compositions.
Such compositions are part of the present invention.
The examples which follow are intended to illustrate the invention, xe2x80x9cactive ingredientxe2x80x9d being understood as meaning a mixture of compound I and compound II (in particular metalaxyl II A, preferably R-metalaxyl II B) in a specific mixing ratio.